CN108699419A

CN108699419A - Including the composition of epobond epoxyn and aluminum slice and the method for preparing it

Info

Publication number: CN108699419A
Application number: CN201780014773.7A
Authority: CN
Inventors: 杰伊·S·施勒希特; 佩顿·R·诺斯比施; 乔治·M·斯托特; 迈克尔·A·克洛普
Original assignee: 3M Innovative Properties Co
Current assignee: 3M Innovative Properties Co
Priority date: 2016-03-02
Filing date: 2017-03-02
Publication date: 2018-10-23
Anticipated expiration: 2037-03-02
Also published as: CN108699419B; EP3423539A4; US20170253779A1; WO2017151898A1; EP3423539A1; CA3016437C; US10683441B2; CA3016437A1; EP3423539B1

Abstract

Curable adhesive composition includes curable epoxy, amine hardener, toughener and aluminum slice.Aluminum slice includes aliphatic acid grinding aid at least a part of the surface thereof.Aluminum slice is heated after milling.This method includes:The aluminum slice with aliphatic acid grinding aid at least a part of the surface thereof is obtained, wherein the aluminum slice had previously been ground;The aluminum slice is heated;And aluminum slice is then made to be mixed with the component comprising amine hardener or curable epoxy.In some embodiments, component also includes toughener.

Description

Including the composition of epobond epoxyn and aluminum slice and the method for preparing it

Cross reference to related applications

This application claims the priority for the U.S. Provisional Application 62/302,720 that on March 2nd, 2016 submits, the disclosure of which It is incorporated by reference herein in its entirety.

Background technology

Adhesive has been used for various structures application.It includes vehicle, computer package, building and utensil that this class formation, which is applied,.Example Such as, construction adhesive has been used for vehicle assembly (such as automobile and aircraft assembling) to substitute or reinforce conventional joining techniques, such as Welding, nuts and bolt and rivet.Epoxy composite is known and is coated for construction adhesive.Toughener includes In epoxy adhesive composition, to improve the impact resistance of adhesive.See, for example, United States Patent (USP) 6,800,157 (Tarbutton et al.).

Aluminum slice has been used as filler to introduce coating and adhesive.See, for example, (the Cussot etc. of United States Patent (USP) 4,920,002 People).Certain aliphatic acid use during grinding aluminum slice as grinding aid sometimes.See, for example, United States Patent (USP) 3,234,038 (Stephens et al.) and 3,181,962 (Rolles) and European patent publication 0015725 (September is announced on the 17th within 1980).

Invention content

Curable compositions according to the present invention include aluminum slice.It was found that aluminum slice may be due to its plate property And tend to the failure mode of driving and the product cohesional failure of adhesives.The cohesional failure at the joint portion of bonding makes adhesive Layer stays on metal, corrodes at the joint portion to limit failure.Our undesirable aluminum slices by influence adhesive impact or Peel strength.It has surprisingly been found that, relative to the adhesive for including aluminum slice not heated after milling, by fat The aluminum slice of fat acid coating heats the peel strength and impact resistance for improving adhesive before introducing adhesive composition.

In one aspect, present disclose provides curable adhesive compositions, and it includes curable epoxy, amine curings Agent, toughener and aluminum slice.Aluminum slice includes aliphatic acid grinding aid at least a part of the surface thereof.Aluminum slice is being ground It is heated after mill.

In some embodiments, curable adhesive composition is packaged as two-part adhesive, wherein first part Including amine hardener, second part includes curable epoxy, and at least one of first part or second part include to increase Tough dose, and at least one of first part or second part include aluminum slice.Therefore, on the other hand, the disclosure provides Adhesive dispenser including the first Room and second Room.First Room includes first part, and second Room includes second part.

On the other hand, present disclose provides a kind of methods forming adhesives object between components.This method packet It includes and foregoing curable adhesive composition is applied on the surface of at least one of two or more components, connecting elements, Between so that curable adhesive composition is clipped in two or more components, and curable adhesive composition is made to consolidate Change, to form adhesives object between two or more components.

On the other hand, the disclosure provides the system for including the curable adhesive composition being clipped between at least two components Product.Curable adhesive composition includes aluminum slice within through the cured toughening epoxy resin of amine hardener.Aluminum slice is in its table It include aliphatic acid grinding aid in at least part in face.Aluminum slice is heated after milling.

On the other hand, the present invention provides at least part of methods for preparing curable adhesive composition.It should Method includes:The aluminum slice with aliphatic acid grinding aid at least a part of the surface thereof is obtained, wherein the aluminum slice Previously it has been ground;The aluminum slice is heated;And then make aluminum slice with comprising amine hardener or curable epoxy tree The component of fat is mixed.In some embodiments, component also includes toughener.

In this application, term such as "one", "an" and "the" be not intended to only refer to single entities, but including can The general category of specific example for illustration.Term "one", "an" and "the" can be mutual with term " at least one (kind) " Change use.The phrase at least one of " ... (kind) " and at least one of " include ... (kind) " for being followed by list be Refer to any combinations of two or more items in any one of project in list and list.Unless otherwise noted, otherwise own Numberical range includes the non integer value between their end value and end value.

Term " solidification " and " curable " refer to, usually by corsslinking molecular or group, and being polymerize by covalent chemical bond Object chain link is together to form network polymers.Therefore, in the disclosure, term " cured " and " crosslinked " can be interchanged It uses.Solidification or crosslinked polymer are characterized in that insoluble in general, but can be molten in the presence of suitable solvent Swollen property.

Term " polymer " or polymerization " polymer, copolymer are will be understood to comprise (for example, using two or more The polymer that different monomers are formed), oligomer or monomer and combination thereof that polymer can be formed, and can be total to Mixed polymer, oligomer, monomer or copolymer.

" alkyl group " and prefix " alkane-" are comprising straight chain and branched group and cyclic group.In some embodiment party In case, unless otherwise specified, (in some embodiments, at most 20,15,12, alkyl group has at most 30 carbon 10,8,7,6 or 5 carbon).Cyclic group can be monocycle or polycyclic, and in some embodiments, have 3 to 10 Ring carbon atom.End " alkenyl " group has at least three carbon atom.

" alkylidene " is multivalence (such as divalent or trivalent) form of " alkyl " group as defined above.

" aryl alkylene " refers to that aryl group is attached to " alkylidene " part thereon." alkyl arylene " refers to alkyl Group is attached to " arlydene " part thereon.

As used herein, term " aryl " and " arlydene " include homocyclic aromatic ring or member ring systems, for example, having 1,2 or 3 A ring and in ring optionally contain at least one hetero atom (for example, O, S or N), the ring optionally by most five replace Base is replaced, which includes one or more alkyl groups (for example, methyl or ethyl) at most 4 carbon atoms, Alkoxy, halogen (that is, fluorine, chlorine, bromine or iodine), hydroxyl at most 4 carbon atoms or nitro.The example packet of aryl group Include phenyl, naphthalene, xenyl, fluorenyl and furyl, thienyl, pyridyl group, quinolyl, isoquinolyl, indyl, iso-indoles Base, triazolyl, pyrrole radicals, tetrazole radical, imidazole radicals, pyrazolyl, oxazolyls and thiazolyl.

The above-mentioned general introduction of the disclosure is not intended to each of the description disclosure open embodiment or each realization method.With Exemplary embodiment more specifically has been illustrated in lower description.It should not be construed as it will thus be appreciated that being described below To the improper restriction of disclosure range.

Specific implementation mode

It can be used for according to the epoxide of the curable compositions of the disclosure including aromatic polyepoxide resin (example Such as, the dicyclic oxide of chain elongation or the novolac epoxy resin at least two epoxy groups) and aromatic monomer diepoxy Compound.Crosslinkable epoxy resin is usually epoxy-terminated at least two.Aromatic polyepoxide or aromatic monomer diepoxy Compound, which generally comprises, is optionally optionally substituted by halogen at least one (in some embodiment party of (such as fluoro, chloro, bromo, iodo) In case, at least two, in some embodiments, in the range of 1 to 4) aromatic ring, alkyl with 1 to 4 carbon atoms (such as Methyl or ethyl) or hydroxyalkyl (such as methylol) with 1 to 4 carbon atom.For including two or more aromatic rings Epoxy resin, the ring can (for example) (optionally can quilts by branch with 1 to 4 carbon atom or straight chain alkylen Halogen replaces (e.g., fluoro, chloro, bromo, iodo)) connection.

The example that can be used for the aromatic epoxy resin of curable compositions disclosed herein includes novolac epoxy resin (example As phenol-phenolic aldehyde, neighbour, partially or paracresol-phenolic aldehyde or combination thereof), bisphenol epoxy it is (such as bisphenol-A, Bisphenol F, halogenated Bisphenol epoxy and combination thereof), resorcinol type epoxy, tetraphenyl ethylene epoxy resin (tetrakis Phenylolethane epoxy resins) and any of these combinations.Available epoxide includes bifunctional phenol Diglycidyl ether (such as p, p '-dihydroxy dibenzyl, p, p '-dihydroxydiphenyls, p, the p '-dihydroxy benzenes of class compound Base sulfone, p, p '-dihydroxy benaophenonels, 2,2 '-dihydroxy -1,1- dinaphthyl methanes and dihydroxydiphenyl methane, dihydroxy Diphenyldimethyhnethane, dihydroxydiphenyl methylmethane, dihydroxydiphenyl methyl-propyl methane, dihydroxydiphenyl second Base phenylmethane, dihydroxydiphenyl propyl phenylmethane, dihydroxydiphenyl butyl phenyl methane, dihydroxydiphenyl toluene Base ethane, dihydroxydiphenyl tolylmethyl methane, dihydroxydiphenyl dicyclohexyl methyl hydride and dihydroxydiphenyl ring are The 2 of alkane, 2 ', 2,3 ', 2,4 ', 3,3 ', 3,4 ' and 4,4 ' isomers).In some embodiments, adhesive includes that bis-phenol two contracts Water glycerin ether, wherein bis-phenol is (that is,-O-C₆H₅-CH₂-C₆H₅- O-) can be unsubstituted (for example, Bisphenol F) or benzyl ring Or any one of methylene group can be by one or more halogens (for example, fluorine, chlorine, bromine, iodine), methyl group, fluoroform Base group or methylol groups substitution.

It can be used for including bisphenol-A according to the example of the aromatic monomer dicyclic oxide of the curable compositions of the disclosure and double The diglycidyl ether of phenol F and their mixture.Bisphenol epoxy for example can chain elongation with any desired ring Oxygen equivalent.Chain elongation epoxy resin can for example, by making monomer dicyclic oxide react progress in the presence of a catalyst with bis-phenol, To prepare linear polymer.

In some embodiments, aromatic epoxy resin (such as bisphenol epoxy or novolac epoxy resin) can have extremely The epoxy equivalent weights of few 150,170,200 or 225 grams/equivalent.In some embodiments, aromatic epoxy resin can have The epoxy equivalent weights of most 2000,1500 or 1000 grams/equivalent.In some embodiments, aromatic epoxy resin can have Epoxy equivalent weights in 150 to 2000,150 to 1000 or 170 to 900 grams/equivalent weight range.In some embodiments, One epoxy resin has the epoxy equivalent weights in 150 to 450,150 to 350 or 150 to 300 grams/equivalent weight range.Epoxy is worked as Amount weight can for example be selected such that epoxy resin is used as desired as liquid or solid.

To may be useful in the epoxy network of flexible non-aromatic chain introducing crosslinked for some applications.In some feelings Under condition, nonaromatic epoxy resin can be used as reactive diluent, can help to the flow behavior of control adhesive composition.It can use It may include branch or straight chain alkylen in the nonaromatic epoxy resin of the curable compositions according to the disclosure, have optional 1 to 20 carbon atom that ground is interrupted and is optionally optionally substituted by a hydroxyl group by least one-O-.In some embodiments, non-aromatic Epoxy resin may include poly- (alkylidene oxide) group, have multiple (x) oxyalkylene group OR¹, wherein each R¹Independently For C₂To C₅Alkylidene, in some embodiments, C₂To C₃Alkylidene, x are 2 to about 6,2 to 5,2 to 4 or 2 to 3.In order to become It must be cross-linked into network, available nonaromatic epoxy resin is usually epoxy-terminated at least two.Available aromatic epoxy tree The example of fat includes glycidyl epoxies, is such as shunk based on two including one or more oxyalkylene units sweet Those of oil base ether compound.These examples include by ethylene glycol diglycidyl base ether, propylene glycol diglycidyl ether, two Glycol diglycidyl ether, dipropylene glycol diglycidyl ether, polyethylene glycol diglycidyl base ether, polypropylene glycol two contract Water glyceryl ether, glycerine diglycidyl ether, T 55, propylene glycol diglycidyl ether, butanediol two Resin made of glycidyl ether and hexylene glycol diglycidyl ether.Other available nonaromatic epoxy resins include The diglycidyl ether of cyclohexanedimethanol, the diglycidyl ether of neopentyl glycol, trimethylolpropane tris glycidol The diglycidyl ether of base ether and 1,4-butanediol.In some embodiments, nonaromatic epoxy resin is to be based on to consolidate Change the total weight up to 20 (in some embodiments, 15,10,9,8,7,6 or 5) of adhesive composition epoxy resin Weight % exists.

Cross-linked aromatic epoxides (i.e. epoxy polymer) as described herein is it will be appreciated that by making aromatic epoxy resin It is crosslinked to prepare.Crosslinked aromatic epoxy resin generally comprises repetitive unit, has optionally by one or more halogen (examples Such as fluoro, chloro, bromo, iodo), alkyl with 1 to 4 carbon atoms group (such as methyl or ethyl) or have 1 to 4 At least one (in some embodiments, at least two of hydroxyalkyl group (such as methylol) substitution of carbon atom;At some In embodiment, in the range of 1 to 4) aromatic ring (such as phenyl group).For the repetition list comprising two or more aromatic rings Member, the ring can (for example) (can optionally be taken by branch with 1 to 4 carbon atom or straight chain alkylen by halogen Generation (e.g., fluoro, chloro, bromo, iodo)) connection.

It can be used for commercially available according to several curable epoxies of the curable compositions of the disclosure.For example, each Several epoxy resin of kind classification and epoxy equivalent weights are purchased from the Dow Chemical (Dow of available Chemical Company, Midland, Mich.);The Mai Tute of Columbus, Ohio chemical company (Momentive Specialty Chemicals, Inc., Columbus, OH);The Hensel of Texas Wood orchid hereby steps advanced material (Huntsman Advanced Materials, The Woodlands, Tex);The special chemistry of CVC in Ohio Akron city Product company (CVC Specialty Chemicals Inc.Akron, OH) is (by Emerald performance materials company (Emerald Performance Materials) obtain);And Taibei City, Taiwan Nan Ya Plastics joint-stock company (Nan Ya Plastics Corporation, Taipei City, Taiwan).The example of commercially available glycidol ether includes the two of bisphenol-A Glycidol ether (such as derives from Germany with trade name " EPON 828 ", " EPON 1001 ", " EPON 1310 " and " EPON 1510 " Hexion Specialty Chemical product limited liability company of Rossbacher city (Hexion Specialty Chemicals GmbH Those of (Rosbach, Germany)), Dow Chemical (Dow Chemical Co.) is derived from trade name " D.E.R. " Those (such as D.E.R.331,332 and 334) derive from Dainippon Ink. & Chemicals Inc with trade name " EPICLON " Those of (Dainippon Ink and Chemicals, Inc.) (such as EPICLON 840 and 850);With with trade name " YL- 980 " derive from those of Japanese epoxy resin Co., Ltd (Japan Epoxy Resins Co., Ltd.s));Two contractings of Bisphenol F Water glycerin ether (such as Dainippon Ink and Chemicals, those of Inc. (examples can be derived from trade name " EPICLON " Such as " EPICLON 830 "));Polyglycidyl ether (such as novolac epoxy resin, such as can be with trade name of novolac resin " D.E.N. " derive from those of Dow Chemical (Dow Chemical Co.) (e.g., D.E.N.425,431 and 438));And Fire-retardant epoxy resin (such as " D.E.R.580 ", a kind of brominated bisphenol type epoxy resin being purchased from Dow Chemical).It is commercially available Nonaromatic epoxy resin example include cyclohexanedimethanol glycidyl ether, with trade name " HELOXY MODIFIER 107 " are purchased from Hexion special chemical article limited liability company (Hexion Specialty Chemicals GmbH).

Curable adhesive composition includes the amine hardener that can make cross linking of epoxy resin.Amine hardener includes at least two A amino group, and can be aromatics, aliphatic series (such as line style or alicyclic) or combination thereof.Amino in amine hardener Group is each independently primary or secondary amino group.In general, at least one amino group is primary amino groups so that friendship can be formed Networking network.In some embodiments, amine hardener includes at least two primary amino groups.

Available amine hardener can be the aliphatic amine for including at least two amino groups.In some embodiments, alkylene Quito amine, such as the alkylene polyamine of linear chain or branched chain are included in curable compositions.Available alkylene polyamine includes second Enamine (such as ethylenediamine, diethylenetriamines, trien etc.), propylamine (such as dimethylamino propylamine, lignocaine third Amine and Cyclohexylamino propylamine), advanced Alkylenediamine (such as hexamethylene diamine, methyl pentamethylene diamine, Yi Jisan Methyl hexane diamines), polyetheramine (such as polyoxyalkylene diamines, the polyoxypropylene diamine and 4 of such as various molecular weight, 7, 10- trioxas -1,13- tridecane diamine).

The amine hardener that can be used for curable compositions disclosed herein may include at least two amino groups and extremely A few aromatic ring.Amine hardener can be aromatic polyamine, wherein amino group indirect linkage to aromatic ring;Or aryl alkylene polyamine, Wherein amino group is bonded to alkylidene group, which is then bonded to aromatic ring.Amine hardener also may include two Or more aromatic ring and at least two amino groups.In any of these embodiments, aromatic ring can be it is unsubstituted or By one or more halogens (such as fluoro, chloro, bromo, iodo), alkyl with 1 to 4 carbon atoms group (such as methyl Or ethyl) or with 1 to 4 carbon atom hydroxyalkyl group (such as methylol) substitution.For including two or more virtues The amine of ring, the ring can for example (optionally can be by one by branch with 1 to 4 carbon atom or straight chain alkylen Or multiple halogens (such as fluoro, chloro, bromo, iodo), oxygen, sulphur or sulfone group substitution) be indirectly connected with or connect.Including extremely The example of the suitable amine hardener of few two amino and at least one aromatic ring includes phenylenediamine (such as m-phenylene diamine (MPD) or to benzene two Amine), diethyl toluene diamine (such as with its any isomeric forms), diaminotoluene (such as 2,3- diaminotoluenes and 3, 4- diaminotoluenes and methyl-m-phenylene diamines), 1,2- diamino -3,5- dimethyl benzene, 4,5- dimethyl -1,2- benzene two Amine, 2,4,6- trimethyls-m-phenylene diamine (MPD), 2,3,5,6- tetramethyl-p-phenylenediamine, amino-benzylamine (such as 2- amino-benzylamines and 4- Amino-benzylamine), it is ethylenebis aniline, 2,2 '-benzidines, diaminodiphenylmethane, diamino diphenyl sulfone, substituted halogenated Phenylenediamine (such as chloro- 1, the 3- diaminobenzenes of 4-, chloro- 1, the 2- diaminobenzenes of 4- and bromo- 1, the 2- diaminobenzenes of 4-), benzene dimethylamine (such as o- benzene dimethylamine or m-xylene diamine) and 4- (2- amino-ethyls) aniline.

The amine hardener that can be used for curable compositions disclosed herein may include at least two amino groups and at least One aliphatic ring.Can be by amino group indirect linkage to aliphatic ring, or amino group can be bonded to linear chain or branched chain Alkylidene group, the alkylidene group are then bonded to aliphatic ring.Amine hardener also may include that two or more are alicyclic Ring and at least two amino groups.In any of these embodiments, aliphatic ring can be it is unsubstituted or by one or Multiple halogens (such as fluoro, chloro, bromo, iodo), linear chain or branched chain with 1 to 4 carbon atom alkyl group (such as Methyl or ethyl) or with 1 to 4 carbon atom hydroxyalkyl group (such as methylol) substitution.In any of these embodiments In, aliphatic ring can be the carbocyclic ring for not including hetero atom (such as sulphur or nitrogen).For including two or more aliphatic rings Amine, the ring can for example (optionally can be by one or more by branch with 1 to 4 carbon atom or straight chain alkylen A halogen (such as fluoro, chloro, bromo, iodo), oxygen, sulphur or sulfone group substitution) it is indirectly connected with or connects.Including at least two The example of the suitable amine hardener of a amino group and at least one alicyclic group is as described above comprising at least two amino The product of any amine hardener of group and at least one aromatic ring hydrogenated completely or partially.For example, suitable amine hardener packet Include diaminocyclohexane (such as 1,2- diaminocyclohexanes or Isosorbide-5-Nitrae-diaminocyclohexane of its cis or trans form) and 3- amino-ethyls -3,5,5- trimethyl cyclohexylamines (also referred to as isophorone diamine).

Several amine hardeners including at least two amino groups and at least one aromatic ring or aliphatic ring can for example derived from The Long Sha groups (Lonza, Basel, Switzerland) of Basel, SUI and the An Bailai of Louisiana Baton Rouge Special company (Amberlite Corporation, Baton Rouge, LA).Available other amine hardeners include polyetheramine, example Such as with trade name " JEFFAMINE " derive from Texas Wood orchid hereby hunter chemical company (Huntsman Chemical, The Woodlands, Tex.).

In some embodiments, on curable epoxy on epoxy group and amine hardener the molar ratio of amine hydrogen about In the range of 0.5: 1 to about 3: 1, in some embodiments, in the range of about 0.5: 1 to about 2: 1 or about 1: 1.

To usually there is the crosslink unit being expressed from the next with the cured epoxy resin of amine hardener:

Wherein R is aryl as described above, alkylene-aryl-alkylene Base, branched alkylidene, straight-chain alkyl-sub or cycloalkylene group optionally include ehter bond, and wherein * instructions O is bonded to ring Oxygen resin matrix is often bonded to aromatic ring, but in some embodiments, is bonded to aliphatic ring or has as described above and appoints The alkylidene group of the branch of 1 to 20 carbon atom or straight chain that selection of land is interrupted and is optionally optionally substituted by a hydroxyl group by least one-O-.

In some embodiments, curable adhesive composition is packaged as two-part adhesive, wherein first part Including amine hardener, and second part includes curable epoxy.First part can be described as " promoter component ", and can Including curing agent and any catalyst.Second part can be described as " base resin component ", and may include any curable resin. The other components for the curable adhesive composition being detailed further below may include in one of first and second parts or two In person.The disclosure also provide include the first Room and second Room adhesive dispenser.First Room includes first part, and second Room Including second part.

Include toughener according to the curable adhesive composition of the disclosure.Toughener can be used for for example improving some solidifications The characteristic (such as peel strength) of epoxy resin so that brittle fracture failure does not occur for they.Toughener (such as elastomer resin Or elastomer-filled dose) can with or can not be final to crosslinked network covalently bonded to curable epoxy.In some implementations In scheme, toughener includes the compound of epoxy radicals end-blocking, be may be incorporated into main polymer chain.Available toughener (can also claim For elastomer modifier) example include the polymerization with both rubber phase and thermoplasticity phase compound, such as:With polymerization Diene rubber core and polyacrylate or polymethacrylates shell graft copolymer;With rubbery kernel and polypropylene The graft copolymer of acid esters or polymethacrylates shell;In the elastomer of epoxides and in-situ polymerization in copolymerization stabilizer Grain, monomer of the epoxides from free redical polymerization;Elastomer molecules, such as polyurethane and thermoplastic elastomer (TPE);It is single Only elastomer precursor molecule;Combination molecule including epoxy resin segment and elastomer segment;And such independent and combination The mixture of molecule.Combination molecule can be prepared by making following item reaction:Epoxide resin material and elastomer segment;Reaction is stayed Reactive functional groups are descended, unreacted epoxy group in such as reaction product.

The toughener used in epoxy resin is described in chemical progress book series (Advances in Chemistry Series), No. 208, entitled " thermosetting resin (the Rubbery-Modified Thermoset of modified rubber Resins) ", edited by C.K.Riew and J.K.Gillham, American Chemical Society, the State of Washington (American Chemical Society, Washington), 1984.The final physical that the amount of toughener to be used depends in part on desired solidified resin is special Property, and generally according to empirically determined.

In some embodiments, the toughener in curable epoxy include with polymerization diene rubber main chain or The graft copolymer of core, be grafted on the main chain or core acrylate or methacrylate, monovinyl aromatic hydrocarbons or The shell of their mixture, such as United States Patent (USP) 3, those of disclosed in 496,250 (Czerwinski).Rubber backbone can wrap The polyblend of butadiene or butadiene and styrene containing polymerization.Including the shell of the methacrylate of polymerization can be low Grade alkyl (C_1-4) methacrylate.Monovinyl aromatic hydrocarbon can be styrene, α-methylstyrene, vinyltoluene, ethylene Base dimethylbenzene, vinyl xylene, ethyl vinyl benzene, isopropyl styrene, chlorostyrene, dichlorostyrene and ethyl chlorostyrene.

Can be that acrylate core-shell graft copolymer, center or main chain turn for vitrifying with the other example of toughener Temperature (T_g) it is below about 0 DEG C of polyacrylate polymers, such as poly- (butyl acrylate) or poly- (Isooctyl acrylate monomer), On be grafted with about 25 DEG C of T_gPolymethacrylate polymer shell, it is such as poly- (methyl methacrylate).For acrylic compounds Core shell material, " core " will be understood as with T_gThe acrylic polymer that 0 DEG C of <, and " shell " will be understood as with T_g> 25 DEG C of acrylic polymer.Some core shell toughener (such as including acrylic acid core shell material and methacrylate-fourth Styrene (MBS) copolymer, center is crosslinked styrene/butadiene rubbers, and shell is polymethylacrylic acid Ester) with trade name " PARALOID " derive from such as Dow Chemical (Dow Chemical Company).

In addition available core shell rubber is described in U.S. Patent Application Publication 2007/0027233 (Yamaguchi et al.). Core shell rubber particle as described in the document includes:Crosslinked rubbery kernel, it is total for crosslinked butadiene in most cases Polymers;And shell, optimization styrene, methyl methacrylate, glycidyl methacrylate and optional acrylonitrile are total to Polymers.Core shell rubber is dispersed among in polymer or epoxy resin.The example of available core shell rubber includes with trade name Kaneka KANE ACE by Kanegafuchi Chemical Industry Co., Ltd (Kaneka Corporation) sell those of, including Kaneka KANE ACE 15 and 120 series of products, including Kaneka " KANE ACE MX 153 ", Kaneka " KANE ACE MX 154 ", Kaneka " KANE ACE MX 156 ", Kaneka " KANE ACE MX 257 " and Kaneka " KANE ACE MX 120 " core shell rubber dispersions and their mixture.Product includes pre-dispersed in epoxy resin with various concentration Core shell rubber (CSR) particle.For example, " KANE ACE MX 153 " core shell rubber dispersion includes 33%CSR, " KANE ACE 154 " core shell rubber dispersions of MX include 40%CSR, and " KANE ACE MX 156 " core shell rubber dispersion includes 25%CSR.

Other examples that can be used for the toughener of the curable compositions according to the disclosure are elastomer particles, are had T below about 25 DEG C_g, and before other components with curable compositions mix in-situ polymerization in epoxides.This A little elastomer particles by free redical polymerization monomer and dissolve in epoxides the polymerization of copolymerizable Polymeric stabilizers and At.Here free radical polymerizable monomer be ethylenically unsaturated monomers, or with coreactivity difunctionality hydrogen compound (such as two Alcohol, diamines and alkanolamine) combine diisocyanate.The example of these elastomer particles is disclosed in United States Patent (USP) 4,524, 181 (Adam et al.).These particles are commonly referred to as " organosol ".

Other toughener are the liquid epoxies of modified rubber.For example, the ABA type with reactive epoxy groups is embedding Section copolymer elastomer can be reacted with epoxy resin, to provide the liquid epoxies of modified rubber.ABA block copolymer elastomerics Body is usually such elastomer, and wherein A blocks are polystyrene, and B block is conjugated diene (that is, low-grade alkylidene Diene).A blocks are usually mainly by (for example, alkylated) or unsubstituted styrenic moiety for replacing (for example, polyphenyl It is ethylene, poly- (α-methylstyrene) or poly- (t-butyl styrene)) it is formed, average molecular weight is about 4, and 000 gram/mol is extremely 50,000 grams/mol.B block is usually mainly by may replace or unsubstituted conjugated diene is (for example, isoprene, 1,3- fourths two Alkene or Ethylene/Butylene monomer) it is formed, and its average molecular weight is about 5,000 gram/mol to 500,000 gram/mol.Example Such as, A blocks and B block can linear, radial or star configuration construct.ABA block copolymers may include multiple A blocks And/or B block, these blocks can be made of identical or different monomer.The example of this kind of resin is elastomer, with trade name " KRATON RP6565 " is purchased from Ke Teng high-performance polymers company (Kraton Performance Polymers).Modified ring Oxygen resin (obtains) system by the epoxy resin " EPON 828 " of 85 weight % and the rubber of 15 weight % with trade name " KRATON " .It is known as elastomeric block copolymers in the industry with the rubber that trade name " KRATON " obtains.

Other available toughener include the acrylonitrile/butadiene elastomer of carboxyl-and amine sealing end, such as with trade name " HYPRO (such as CTBN and ATBN grades) is obtained from the Emerald performance materials company (Emerald in Ohio Akron city Those of Performance Materials, Akron, OH);The butadiene polymer of carboxyl-and amine sealing end, such as with commodity Name " HYPRO (such as CTBN grades) be obtained from Emerald performance materials company (Emerald Performance Materials, Those of Akron, OH);Amine-functional polyethers, such as it is any of above those;And amine-functional polyurethane, such as it is described in Those of U.S. Patent application 2013/0037213 (Frick et al.).Polyurethane toughened dose may also comprise it is isocyanate-modified Epoxy resin, isocyanate-modified epoxy resin and combination thereof.If isocyanates is directly and epoxy reaction, Then isocyanate-modified epoxy resin Ke have an oxazolidine functional group, or if isocyanates and be present in epoxy molecule Secondary hydroxyl reacts, then isocyanate-modified epoxy resin can have urea/ureido functional group.It can be used as disclosure curable adhesive The example of the isocyanates of toughener in composition or polyurethane-modified epoxy resin includes with trade name " EPU-17T- 6 ", those of " EPU-78-11 " and " EPU-1761 " acquisition, purchased from Chinese mugwort Dicon A/S (Adeka Co.), with trade name " D.E.R.6508 " is purchased purchased from those of Dow Chemical (Dow Chemical Co.), and with trade name " AER 4152 " From those of Asahi Electro-Chemical Co. Ltd (Asahi Denka).

In some embodiments, toughener is acrylic acid core shell polymer;Styrene-butadiene/methacrylate Core shell polymer;Polyether polymer;Carboxyl or amino-terminated acrylonitrile/butadiene;Carboxylated butadiene, polyurethane or they Combination.

In some embodiments, toughener is present in curable with the amount of up to about 75 parts by weight/100 part epoxy resin In composition.In some embodiments, curable adhesive composition includes to be based on 100 parts by weight reactivity epoxy resins Up to 75 parts by weight, in some embodiments, within the scope of about 5 parts by weight to about 75 parts by weight, or about 10 parts by weight are to about 50 Polymer toughener within the scope of parts by weight.For the two-part adhesive composition according to the disclosure, toughener can be added To first part, second part, or both in.If desired, can be pre-dispersed in first part by toughener amine hardener, With/be scattered in second part with epoxy resin prepolymer.

In some embodiments, include catalyst according to the curable resin composition of the disclosure.It is in office what to implement In scheme it is above-mentioned can be used for accelerating the catalyst of epoxy resin cure and the example of amine hardener may include tertiary amine and ring amidine (such as Imidazoles).The example of suitable ring amidine includes imidazoles, imidazoline, substituted imidazolium compounds, substituted imidazolinium compounds, Isosorbide-5-Nitrae, 5,6- tetrahydropyrimidines, substituted Isosorbide-5-Nitrae, 5,6- tetrahydropyrimidine compounds and combination thereof.Suitable tertiary amine includes benzyl two Methylamine, diazabicyclo endecatylene and including phenolic hydroxyl group (such as dimethylaminomethylphenol and three (dimethylamino methyls) Phenol) tertiary amine and combination.In addition suitable catalyst includes being purchased from New Jersey with trade name " VERSAMINE EH 30 " The not tertiary amine of the BASF AG (BASF Corporation, Florham Park, New Jersey) of Lip river Farnham Parker.According to Any proper amount of catalyst can be used in required reaction rate.In some embodiments, it is based on curable adhesive composition Total weight, the amount of catalyst is in 0.1 weight % to 7.5 weight % (in some embodiments, 0.5 weight % to 5 weights Measure %, 0.5 weight % to 3 weight % or 0.5 weight % to 2.5 weight %) within the scope of weight %.For according to the disclosure Catalyst is usually added to first part by two-part adhesive composition.

Curable compositions according to the present invention include aluminum slice.When for adhesive composition, aluminium filler can carry Supply substrate corrosion protection.Aluminum slice is selected for curable compositions according to the present invention, with driving and adhesives Product cohesion break ring failure mode.Think that the plate property of aluminum slice is that cohesional failure pattern is dominant in failure joint portion The reason of.The cohesional failure at the joint portion of bonding makes adhesive phase stay on metal, corrodes at the joint portion to limit failure.

Aluminum slice usually by grinding the alumina particles such as aluminium-foil scrap or aluminium powder in the grinding machine (such as ball mill or stamping mill) and It generates.Grinding can carry out under dry state or hygrometric state (i.e. in the presence of solvent).It can be used for the aluminium of the curable compositions according to the disclosure The grinding product that thin slice is generated generally by dry grinding.Dry grinding refer to there is no organic solvent (such as volatile organic solvent, Such as solvent naphtha) when the grinding implemented.Dry grinding usually carries out in the presence of grinding aid, to improve the stability of aluminum metal and prevent Only aluminum slice aoxidizes.Grinding aid usually remaines on thin slice after grinding, and can be more with the total weight based on aluminum slice Amount to about 5 weight %, 4 weight %, 3 weight % or 2 weight % exists.Heat can be generated during process of lapping.However, will After milling according to the aluminum slice in the adhesive composition of the disclosure, usually in packaging, shipment or storage aluminum slice extremely It is heated after few one.

The grinding aid that can be used for aluminum slice in the curable compositions according to the disclosure is aliphatic acid or aliphatic acid Mixture.Aliphatic acid can indicate by formula RCOOH, wherein R be have about 1 to 30 (in some embodiments, 6 to 26,8 to 26, Or 8 to 22) alkyl group or alkenyl group of a carbon atom.Short chain fatty acids are generally considered to have less than 6 carbon atoms Those, and long chain fatty acids are those of tool 6 or more carbon atoms.Long-chain with eight to 26 carbon atoms is full Common name with aliphatic acid is sad (C8), capric acid (C10), lauric acid (C12), myristic acid (C14), palmitic acid (C16), hard Resin acid (C18), arachidic acid (C20), behenic acid (C22), lignoceric acid (C24) and cerinic acid (C26).Aliphatic acid grinding helps Agent may include the mixture of any of these aliphatic acid.Certain aliphatic acid (such as stearic acid) provide the aluminum slice of float type grade, And other aliphatic acid (such as oleic acid or short chain fatty acids) provide the aluminum slice of non-floating grade.When being scattered in composition When, float type grade, which usually becomes, to be able to arrange relative to surface parallel mode, and non-floating grade tends to have in the composition There is random orientation.In some embodiments, aliphatic acid grinding aid includes stearic acid or its decomposition product.

In the curable compositions according to the disclosure, the routine of aliphatic acid will be included at least a part of the surface thereof The aluminum slice of grinding heats after milling.In the case where the disclosure is without being bound by theory, heating can physical or chemical modification Include the aluminum slice of aliphatic acid.Heating aluminum slice can cause one or more in following effect:The thermogravimetric that thermogravimetric analysis generates Curvilinear motion, the visual appearance variation of adhesive composition before or after curing, is made of curable adhesive composition Adhesives object T- peel strengths or at least one of impact peel strength improvement.Heating can observe these effects It is carried out under any temperature of at least one of fruit.For example, aluminum slice can be higher than at least 75 DEG C, 80 DEG C, 90 DEG C or 100 DEG C It is handled at a temperature of room temperature.In some embodiments, at a temperature in the range of 100 DEG C to 150 DEG C, aluminum slice is existed It is heated after grinding.

Use the Q50 of the TA instruments (TA Instruments, New Castle, Del) derived from Delaware State Newcastle Type thermogravimeter analyzes the aluminum slice sample handled in different ways by thermogravimetry.Institute in following examples 1 The aluminum slice for the heating stated shows that resolution ratio is substantially change at about 240 DEG C and 395 DEG C, and as described in exemplary embodiments A For unheated thin slice tool there are four different variations, the variation at only 395 DEG C is identical as the thin slice heated.Removing is washed with toluene Early stage peak, and the sample of gained shows peak there are two tools, a peak at about 350 DEG C and 395 DEG C of overlap of peaks.At 80 DEG C First peak removed for one week seen in unheated thin slice (about 150 DEG C) is heated, but observed unheated thin slice The other three peak.

Heating aluminum slice can improve impact strength and T- peel strengths at room temperature and -20 DEG C.Surprisingly aluminium is thin Piece will influence impact or the peel strength of adhesive.In some embodiments, according to the curable adhesive composition of the disclosure Object solidification when provide adhesives object, and relative to compare adhesive composition have improve T- peel strengths or change At least one of kind impact peel strength, wherein it is identical as curable adhesive composition to compare adhesive composition, no Same is that the aluminum slice comprising aliphatic acid does not heat after milling at least a part of the surface thereof.

The break surface of visual inspection T- strippings and impact peel sample is shown under the conditions of amplification, not compared to aluminum slice The case where heating, thin slice seem to better disperse after the heating described in aluminum slice following examples 1.

Heating aluminum slice can be by the way that the aluminum slice at least a part of the surface thereof comprising aliphatic acid to be placed in baking oven It carries out, and allows to cool down it, then add it to curable adhesive composition.It at industrial scale, can be by 10 About 50,40,30,20,10 or 5 pounds of aluminum slice is placed in about 220 °F to 250 °F (104.4 DEG C to 121.1 DEG C) temperature in gallon cylinder About 16 hours in the baking oven of degree, then it is allowed to be cooled to room temperature.Repeat the process.The fluctuation of oven temperature can be advised with industry It is associated to implement heating on mould.If it is desired to keep aluminum slice not contaminated, cylinder can loosely be covered and blow-by with capping. It adds it to before curable adhesive composition, heating aluminum slice also can be for example in the small-sized wide-mouth bottle of lab oven To carry out on a small scale.In some embodiments, it is ground in the environment setting of aluminum slice temperature within the scope of 100 DEG C to 150 DEG C It heats later.Environment may be, for example, baking oven.

As shown in the comparison between embodiment 1 and exemplary embodiments A, adhesive combination is added to compared to being included in The adhesive composition for the identical aluminum slice not heated before object, heating aluminum slice leads to -20 DEG C at a temperature of at least 100 DEG C Under the unexpected improvement improvement unexpected more than the impact peel strength at 50% and 23 DEG C of impact peel strength More than 40%.Similarly, compared to being included in the adhesive for being added to before adhesive composition the identical aluminum slice not heated Composition, the improvement that heating aluminum slice causes the T peel strengths at 23 DEG C unexpected at a temperature of at least 100 DEG C is about 18%.

For the two-part adhesive composition according to the disclosure, aluminum slice can be added to first part, second part, Or both in.In some embodiments, aluminum slice is added to first part.

Various additives may include in the curable compositions according to the disclosure, to for example change solidification composition filling Feature.The example of useful additives includes such as certain silica gel of resist, thixotropic agent such as pyrogenic silica;Pigment (example Such as iron oxide, brick dust, carbon black and titanium dioxide), reinforcing agent (such as silica, magnesium sulfate, calcium sulfate and aluminizing silicic acid Salt), clay such as bentonite and any suitable filler (such as bead, talcum and calcium metasilicate).Every 100 parts of liquid Body adhesive component can effectively utilize up to about 30,40,50 parts, or more part additive amount.

In some embodiments, include silane coupling agent according to the composition of the disclosure.Suitable silane coupling agent Example includes by formula L-[R²Si(Y)₃]_kThose of indicate.In the formula, L be amino group (such as primary or secondary amino group), Mercapto groups (i.e. HS-) or epoxy group are (i.e.).Such L groups can be reacted with epoxy resin.In some implementations In scheme, L is epoxy group.In formula L-[R²Si(Y)₃]_kIn, k is usually 1, but when L is amino, and k is 1 or 2.In formula L- [R²Si(Y)₃]_kIn, R²To be optionally inserted into the alkylidene (such as with up to 8,6 or 4 carbon atoms) of at least one ehter bond, And Y is hydrolyzable groups, such as halogen (i.e. fluorine, chlorine, bromine or iodine), alkoxy (i.e.-O- alkyl), acyloxy (i.e.-OC (O) Alkyl) or aryloxy group (i.e.-O- aryl).Silane coupling agent can be used for promoting composition epoxy resin and filler (such as containing Silicon filler) between or epoxy resin and epoxy resin be assigned to the adhesiveness between substrate thereon.It is available silane coupled The example of agent includes 3- glycidoxypropyltrimewasxysilanes, such as with trade name " DOW CORNING Z- 6040SILANE " purchased from available Dow Corning Corporation (Dow Corning Corporation, Midland, Michigan);Bis- (trimethoxy-silylpropyl) amine, for example, be available from Pennsylvania Mo Lisiweier Gillette this Special (Gelest, Morrisville, PA);(3- aminopropyls) trimethoxy silane, (3- aminopropyls) triethoxysilane), (3- mercaptos propyl) trimethoxy silane and (3- mercaptos propyl) triethoxysilane, such as it is available from St. Louis Sigma-Aldrich (Sigma-Aldrich, St.Louis, MO).In some embodiments, curable adhesive composition Object includes 3- glycidoxypropyltrimewasxysilanes.Silane coupling agent can be based on the total weight of adhesive composition Up to 5 weight %, 4 weight %, 3 weight %, 2 weight % or 1 weight % amount be present in curable adhesive composition. Coupling agent including epoxy group can be introduced into the second part of such as two-part adhesive composition.It can will include amino base The coupling agent of group is introduced into the first part of such as two-part adhesive composition.

In some embodiments, curable adhesive composition includes plasticizer.Available plasticizer may include NOT function It can property plasticizer, such as aliphatic series and aromatic hydrocarbon, Arrcostab, alkyl ether, aryl ester and aryl ether.Available plasticizer shows Example includes isodecyl benzoate, and the quotient Ji Nuoweike with trade name " BENZOFLEX " purchased from Illinois State Rosemount public It takes charge of those of (Genovique Specialties Corporation, Rosemont, Illinois).Available plasticizer It may include functional compound, such as alkylol, glycol and glycol ethers.The example of accessible plasticizer includes dimethyl -1 3,3-, 2- epoxy butanes, 1,2- octylene oxides, 1,2- oxepanes, 1,2- epoxy butanes, 1,2- Epoxydodecanes, australene, 2- are pungent Alcohol, 3,3,5- 3-methyl cyclohexanol methyl acrylates, limonene, nopinene, 1,2- decamethylenes, 1,8- cineoles, oxidation Limonene, alpha-oxidation firpene, C1-C10 glycidyl ethers (for example, methyl glycidyl ether, ethyl glycidyl ether, Isopropylglycidyl ether, n-butyl glycidyl ether, isobutyl glycidyl ether, tertiary butyl glycidyl ether with And the air products derived from U.S.'s Allentown and chemical company (Air Products and Chemicals Inc.in Allentown, PA, USA) " EPODIL 746 " and " EPODIL 747 "), the glycidyl ester derivant of versatic acid The hydroxy acrylic acid of (" CARDURA N-10 " it is chemical (Hexion Chemical) to derive from European starfish) and glycidyl esters Ester monomer (" ACE hydroxy-acrylate monomers " derives from starfish chemistry).Plasticizer can be based on the total weight of adhesive composition The amount for counting up to 10 weight %, 5 weight %, 4 weight %, 3 weight %, 2 weight % or 1 weight % is present in curable adhesive In agent composition.For the two-part adhesive composition according to the disclosure, plasticizer can be added to first part, second Point, or both in.In some embodiments (including plasticizer is the embodiment of epoxy-functional plasticizers), by plasticizer It is added to second part.

In some embodiments, curable adhesive composition is two-part adhesive composition.In these embodiment party In some of case, first part may include adduct (48.4wt.% (weight %)) described in following embodiment, 4,7,10- The butadiene third of trioxa -1,13- tridecane diamine (9.0 weight %), m-xylenedimaine (1.8 weight %), amine-sealing end Alkene lonitrile copolymer (7.3 weight %), cycloaliphatic amines (8.2 weight %), tertiary amine (3.0 weight %), calcium carbonate (4.5 weight %), The aluminum slice (4.2 weight %) of heating, aluminium powder (4.2 weight %), wollastonite (3.6 weight %), hydrophobic fumed titanium dioxide Silicon (5.0 weight %) and bead (1.35 weight %).

In some of these embodiments, cycloaliphatic amines are high functionality polycyclic aliphatic polyamine curing agent, with trade name " ANCAMINE 2167 " is purchased from air chemical products Co., Ltd (the Air Products and in Pennsylvania Alan town Chemicals, Inc., Allentown, Pennsylvania);The butadiene acrylonitrile copolymer of amine sealing end is with trade name " HYPRO 1300x21 " is purchased from Emerald performance materials company (the Emerald Performance in Ohio Akron city Materials, Akron, OH);And tertiary amine is Tertiary amine accelerators, and New Jersey is purchased from trade name " VERSAMINE EH 30 " The BASF AG (BASF Corporation, Florham Park, New Jersey) of state not Lip river Farnham Parker.M-phenylene diamine (MPD) Can be commercially available from various sources, including New York Mitsubishi Gas Chemical u s company (Mitsubishi Gas Chemical Company America, Inc., New York, New York).Calcium metasilicate (wollastonite) can be commercially available from various sources, Include the Nyco mineral products company (Nyco of the Weir Si Baoluo with trade name " NYAD G " and " NYGLOS " purchased from New York Minerals, Inc., Willsboro, New York).Aluminum slice and aluminium powder can be commercially available from respective source, including Kentucky Eckart America Corporation (Eckart America Corporation, Louisville, Kentucky) of state Louisville can Various sources are purchased from for reducing contraction and increasing the calcium carbonate of corrosion resistance, include the Ou meter Ya public affairs of Seleznyov Tuttlingen, Switzerland It takes charge of (Omya (Oftringen, Switzerland)).The calcium carbonate (" NPCC-361 " grade) of nanoprecipitation is purchased from a nanometer material Material technology (Singapore) (NanoMaterials Technology (Singapore)), and winnofil (" CALPREC PE " grades) it is purchased from Cales the de Llierca, S.A. of Spain He Luona (Girona, Spain).Fumed silica Silicon available from commercial source, such as the Bostonian Cabot Co., Ltd in Massachusetts (Cabot Corporation, Boston, Mass).With trade name " SHIELDEX AC5 " be obtained from Columbia, MD Grace Dai Weisen (Grace Davison, Columbia, Maryland) the synthesis amorphous silica containing calcium hydroxide be reported can be used for it is anticorrosive.

It is some embodiments of two-part adhesive composition in curable adhesive composition, second part is with quotient " 3M IMPACT RESISTANT STRUCTURAL ADHESIVE, 200ML CARTRIDGE, 07333 " is bright purchased from the U.S. for the name of an article The composition of the 3M companies (3M Company, St.Paul, Minnesota) of the Dazhou City Ni Su Sao Paulo City.In some embodiments In, the first part of two parts curable adhesive composition and second part can be mixed with 1: 2 volume ratio.

It is some embodiments of two-part adhesive composition in curable adhesive composition, second part includes double Phenol A epoxy resin can be purchased from such as Hexion Specialty Chemical company (Hexion Specialty with trade name " EPON 828 " Chemicals);40% core shell rubbers in unmodified liquid epoxies based on bisphenol-A, with trade name " KANE ACE MX 154 " be obtained from the Texas Ka Naika company of Texas Pasadena city (Kaneka Texas Corporation, Pasadena, Texas);3- glycidoxypropyltrimewasxysilanes, such as purchased from DOW CORNING (Dow Corning);Fat Race's epoxy resin, such as cyclohexanedimethanol diglycidyl ether are obtained from Hexion special type with trade name " HELOXY 107 " Company (Hexion Specialty Chemicals), calcium carbonate;Synthesis amorphous silica containing calcium hydroxide, with Trade name " SHIELDEX AC5 " is obtained from Grace Dai Weisen (Grace Davison);Phenolphthalein, as solidification indicator;Pyrolysis Method silica;And plasticizer, such as isodecyl benzoate plasticizer, she is derived from trade name " BENZOFLEX 131 " Sharp promise state Rosemount Shang Ji promises Virbac (Genovique Specialties Corporation, Rosemont, Illinois)。

In some embodiments, curable adhesive composition can be made to heat at elevated temperatures to influence to cure. Although it is unpractical to enumerate suitable for the actual temp of all situations, in general, suitable temperature at about 30 DEG C extremely In the range of about 200 DEG C.In some embodiments, two parts composition is provided as according to the adhesive composition of the disclosure. In general, two kinds of components of two component adhesive are mixed before being applied to base material to be bonded.After mixing, double groups Divide adhesive to be gelled, reaches required processing intensity, finally realize required final strength.Some two-part adhesives can High temperature is exposed to cure, or is at least cured within the required time.In some embodiments, it is heated at 60 DEG C to 80 DEG C It can for example be used within 15 minutes to 60 minutes accelerate solidification.However, in some embodiments, according to the curable composition of the disclosure Object need not heat to cure (i.e. it is room-temperature-curable adhesive), but still provide the higher property of peel strength and impact resistance Energy.

Similarly, according in some of disclosed method embodiments, curable adhesive composition is two parts Adhesive, wherein first part include amine hardener, and second part includes curable epoxy, first part or second part At least one of include toughener, and at least one of first part or second part include aluminum slice.Application can consolidate Changing adhesive composition can be for example curable by being distributed from the adhesive dispenser including the first Room, second Room and mixing tip Adhesive composition carries out, wherein the first Room includes first part, wherein second Room includes second part, and wherein the first He Second Room is connected to mixing tip, to allow first part and second part to flow through mixing tip.

In some embodiments according to the product of the disclosure, product has to take up an official post what described in embodiment Solidification quality adhesive composition the adhesives object first surface and second surface that are connected that prepare.Solidification bonding Agent includes aluminum slice within through the cured toughening epoxy resin of amine hardener.Aluminum slice wraps at least a part of the surface thereof Fatty acids grinding agent, and aluminum slice heats after milling.Curable adhesive composition can be used in metal component (example Such as iron, aluminium, titanium, magnesium, copper and their alloy) between, non metallic substrate (such as strengthens or nonreinforcement thermoplasticity and heat Solidity polymer and other organic materials or organic composite material) between and metal and non metallic substrate between formed it is viscous Mixture adhesive.At least part of vehicle can be formed according to the disclosure and/or the product prepared by disclosed method. In some embodiments, curable adhesive composition provides improved T- peel strengths relative to curable adhesive composition is compared Or improved at least one of impact peel strength, wherein the relatively curable adhesive composition and the solidification adhesive group It is identical to close object, the difference is that aluminum slice does not heat after milling.

Adhesive as described herein can be used for for example assembling plank or other laminated structures with framing component.Adhesive It can be used for the tube frame structure in conjunction with plank and hydroforming, accurate alignment position be in using self-localization method holding member It sets, while making adhesive curing.In addition, adhesive can be used for the component of space frame being bonded together.In addition, adhesive can Such as automobile, paddle block will be welded and be bonded on intrusion crossbeam, invade transverse beam assembly to prepare door.Adhesive also may be used The door that car door is bonded for cementability invades transverse beam assembly.Adhesive can also be used for bonding the structural type component (example of automobile As pillar tower is bonded in longitudinal beam).Welding (such as tack welding) or mechanical fasteners can be used for making cohesive paddle block to fix In place, until adhesive curing.It may also be desirable for adhesive to be bonded together the Guan Gang of hydroforming, to prepare Motor space rack components.The other purposes of disclosure adhesive is related to edge and bonds two bases with appropriate mechanical structure Bottom.In edge bonding, adhesive block is formed between the edge for two substrates being closely aligned with.The edge of substrate is with the side of overlapping Formula is bent, and marginal texture is folding or bending over to be formed, and adhesive be present between substrate entire be folding or bending over edge. The marginal texture thus formed can be then (such as infrared radiation, strong by sensing heating or other common methods that are heating and curing Compel ventilation, submergence etc.) solidification.

In adhesives field, adhesive can be formed available viscous by intermediate point, band, diagonal line or will be suitable for Any other geometric format of knot body applies as continuous pearl.Such adhesive setting choosing can be increased by welding .Welding can take spot welding, continuous seam weld or it is any other can with adhesive block coordinate to form mechanically firm connector Welding technique, the connector have enough antifatigue and impact resistance and bearing performance.Such welding can be around or through Adhesives object occurs.The heating of welding can enhance other solidification energy inputs (such as oven-baked, sensing heating etc.).

Some embodiments of the disclosure

In the first embodiment, the disclosure provides curable adhesive composition, and it includes curable epoxy, amine Curing agent, toughener and aluminum slice, wherein aluminum slice include aliphatic acid grinding aid at least a part of the surface thereof, described Aluminum slice heats after milling.

In this second embodiment, present disclose provides the curable adhesive compositions according to the first embodiment Object, wherein curable epoxy include bisphenol epoxy, novolac epoxy resin or combination thereof.

In the third embodiment, present disclose provides the curable adhesives according to first or second embodiment Composition, wherein toughener include at least one in core shell polymer, acrylic polymer, nitrile rubber or polyurethane Person.

In the 4th embodiment, present disclose provides curable viscous described in any one of first to third embodiment Mixture composite, wherein amine hardener include aliphatic diamine, aromatic diamine, aryl alkylene diamines, polyether diamine or they Combination.

In the 5th embodiment, present disclose provides consolidating according to any one of first to fourth embodiment Change adhesive composition, wherein curable epoxy has two or more epoxy groups, and amine hardener has two A or more amine hydrogen, and the molar ratio range of the amine hydrogen in the epoxy group and amine hardener on curable epoxy is About 0.5: 1 to about 3: 1.

In a sixth embodiment, present disclose provides consolidating according to any one of first to the 5th embodiment Change adhesive composition, wherein curable adhesive composition can be cured at room temperature.

In the 7th embodiment, present disclose provides consolidating according to any one of first to the 6th embodiment Change adhesive composition, wherein aluminum slice heats at a temperature in the range of 100 DEG C to 150 DEG C after grinding.

In the 8th embodiment, present disclose provides consolidating according to any one of first to the 7th embodiment Change adhesive composition, wherein aliphatic acid grinding aid includes stearic acid.

In the 9th embodiment, present disclose provides consolidating according to any one of first to the 8th embodiment Change adhesive composition, wherein aluminum slice is dry grinded.

In the tenth embodiment, present disclose provides consolidating according to any one of first to the 9th embodiment Change adhesive composition, wherein curable adhesive composition provides adhesives object in solidification, and relative to comparing Adhesive composition has improved T- peel strengths or improved at least one of impact peel strength, wherein the comparison is viscous Mixture composite is identical as the curable adhesive composition, the difference is that aluminum slice does not heat after milling.

In the 11st embodiment, present disclose provides according to any one of first to the tenth embodiment can Curable adhesive composition is packaged as two-part adhesive, and wherein first part includes amine hardener, and second part includes Curable epoxy, at least one of first part or second part include toughener, and first part or second Point at least one of include aluminum slice.

In the 12nd embodiment, present disclose provides the curable adhesive groups according to the 11st embodiment Object is closed, is wrapped into the adhesive dispenser including the first Room and second Room, wherein the first Room includes first part, and Wherein second Room includes second part.

In the 13rd embodiment, present disclose provides the method for forming adhesives object between components, the party Method includes:

Curable adhesive composition according to any one of claim 1 to 12 is applied to two or more In component at least one surface;

Connecting elements, to make curable adhesive composition be clipped between two or more components;And

Curable adhesive composition is set to cure, to form adhesives object between two or more components.

In the 14th embodiment, present disclose provides the method according to the 13rd embodiment, two of which Or more at least one of component include at least part of vehicle.

In the 15th embodiment, present disclose provides the method according to the 13rd or the 14th embodiment, Wherein at least one of the T- peel strengths of adhesives object or impact peel strength are improved relative to comparative approach, The comparative approach is identical as the method according to claim 11, the difference is that use compares adhesive composition rather than can Curable adhesive composition, wherein it is identical as curable adhesive composition to compare adhesive composition, unlike aluminum slice It does not heat after milling.

In the 16th embodiment, present disclose provides according to described in any one of the 13rd to the 15th embodiment Method, carried out at room temperature wherein curing.

In the 17th embodiment, present disclose provides according to described in any one of the 13rd to the 16th embodiment Method, wherein curable adhesive composition is two-part adhesive, wherein first part include amine hardener, second part Including curable epoxy, at least one of first part or second part include toughener, and first part or the At least one of two parts include aluminum slice, wherein it includes by curable adhesive composition from including the first Room, the to apply The adhesive dispenser at two Room and mixing tip is allocated, wherein the first Room includes first part, wherein second Room includes the Two parts, and wherein the first and second Room are connected to mixing tip, it is mixed to allow first part and second part to flow through Close tip.

In the 18th embodiment, the disclosure provides a kind of product, and it includes be clipped in consolidating between at least two components Change adhesive composition, curable adhesive composition includes aluminum slice within through the cured toughening epoxy resin of amine hardener, Wherein aluminum slice includes aliphatic acid grinding aid at least a part of the surface thereof, and aluminum slice heats after milling.

In the 19th embodiment, present disclose provides the products according to the 18th embodiment, wherein curing Relative to comparing, curable adhesive composition provides improved T- peel strengths to adhesive composition or improved impact peel is strong At least one of degree, wherein it is identical with curable adhesive composition to compare curable adhesive composition, the difference is that aluminum slice It does not heat after milling.

In the 20th embodiment, present disclose provides the product according to the 18th or the 19th embodiment, Wherein product is a part for vehicle.

In the 21st embodiment, the present invention provides prepare at least part of of curable adhesive composition Method, this method include:

The aluminum slice for including aliphatic acid grinding aid at least a part of the surface thereof is obtained, wherein the aluminum slice is first It is preceding to be ground;

The aluminum slice is heated;And then

The aluminum slice is set to be mixed with the component comprising amine hardener or curable epoxy.

In the 22nd embodiment, present disclose provides the methods according to the 21st embodiment, wherein Component also includes toughener.

In the 23rd embodiment, present disclose provides the methods according to the 22nd embodiment, wherein Toughener includes at least one of core shell polymer, acrylic polymer, nitrile rubber or polyurethane.

In the 24th embodiment, present disclose provides any one of the 21st to the 23rd embodiment institutes The method stated, wherein component include amine hardener, and the amine hardener includes aliphatic diamine, aromatic diamine, aryl alkylene two Amine, polyether diamine or combinations thereof.

In the 25th embodiment, present disclose provides according to any in the 21st to the 23rd embodiment Method described in, wherein component include curable epoxy, and wherein curable epoxy includes bisphenol epoxies tree Fat, novolac epoxy resin or combination thereof.

In the 26th embodiment, present disclose provides according to any in the 21st to the 25th embodiment Described in method, wherein component also include resist, plasticizer, silane coupling agent, thixotropic agent, pigment, reinforcing agent, clay, Or at least one of filler.

In the 27th embodiment, present disclose provides according to any in the 21st or the 26th embodiment Method described in, carries out wherein heating at a temperature in the range of 100 DEG C to 150 DEG C.

In the 28th embodiment, present disclose provides according to any in the 21st to the 27th embodiment Method described in, wherein aliphatic acid grinding aid includes stearic acid.

In the 29th embodiment, the present invention provides any one of the 21st to the 28th embodiment institutes The method stated, wherein aluminum slice were previously dry grinded.

In the 30th embodiment, described in any one of the 21st to the 29th embodiment Method, carried out after packaging, shipment or storage at least one of aluminum slice wherein heating.

In the 31st embodiment, described in any one of the 21st to the 30th embodiment Method, further include that at least part of curable adhesive composition is packaged as two-part adhesive, wherein first Subpackage contains amine hardener, and second part includes curable epoxy, and at least one of first part or second part include Toughener, and at least one of first part or second part include aluminum slice.

In the 32nd embodiment, the disclosure provides the method according to the 31st embodiment, wherein wrapping Dress includes that at least part of curable adhesive composition is introduced into the adhesive dispenser including the first Room and second Room, Wherein the first Room includes first part, and wherein second Room includes second part.

In the 33rd embodiment, present disclose provides according to described in the 31st or the 32nd embodiment Method, wherein curable epoxy have two or more epoxy groups, and amine hardener has two or more Amine hydrogen, and the molar ratio range of the amine hydrogen in the epoxy group and amine hardener on curable epoxy be about 0.5: 1 to About 3: 1.

In the 34th embodiment, present disclose provides according to any in the 21st to the 33rd embodiment Method described in, wherein curable adhesive composition can be cured at room temperature.

In the 35th embodiment, present disclose provides according to any in the 21st to the 34th embodiment Method described in, wherein heating aluminum slice provides adhesives object, and phase in cure curable adhesive composition There is improved T- peel strengths or improved at least one of impact peel strength for comparing adhesive composition, wherein The relatively adhesive composition is identical as the curable adhesive composition, the difference is that aluminum slice is not added with after milling Heat.

In order to which the disclosure can be more fully understood, it is listed below embodiment.It should be appreciated that these embodiments only for into The schematical explanation of row, and should not be construed as limiting the disclosure in any way.

Embodiment:

Following abbreviation is for describing embodiment:

℃:Degree Celsius

°F:Degrees Fahrenheit

J:Joule

Kg:Kilogram

KPa:KPa

L:It rises

lbs:Pound

mL:Milliliter

mm:Millimeter

mm/min:Mm/min

nm:Nanometer

N/mm:Newton/millimeter

rpm:Rev/min

Unless in addition report, otherwise all ratios are by dry weight.

The abbreviation of the material and reagent that are used in embodiment is as follows:

AL-FLK:Aluminum slice is obtained from Kentucky State Louisville's with trade name " ALUMINUM NDT 62540/G " Eckart America Corporation (Eckart America Corporation, Louisville, Kentucky).

AL-PWDR:Aluminium powder is obtained from Eckart America Corporation with trade name " ALUMINUM POWDER 120ATOMIZED " (Eckart America Corporation)。

BFLEX-131:Isodecyl benzoate plasticizer derives from Illinois State sieve with trade name " BENZOFLEX 131 " Shang Ji promises Virbac (Genovique Specialties Corporation, Rosemont, Illinois) of Si Mengte.

EPON-828:The diglycidyl ether of bisphenol-A, wherein approximate epoxide equivalent is 187.5 grams/equivalent, with trade name " EPON-828 " derive from Texas Houston Hexion special type chemical company (Hexion Specialty Chemicals, Houston, Texas).

GB-4:Bead is obtained from Pennsylvania More text with trade name " GLASS BEADS.010IN CLASS 4 " Potler's industry Co., Ltd (Potters Industries, LLC, Malvern, Pennsylvania).

MISTRON:High-purity talc is obtained from the auspicious Xing Neng &amp of Aim with trade name " MISTRON MONOMIX ";Filter minerals (Imerys Performance&Filtration Minerals)。

MX-154:40% core shell rubbers in unmodified liquid epoxies based on bisphenol-A, with trade name " Kane Ace MX 154 " are obtained from the Texas Ka Naika company of Texas Pasadena city (Kaneka Texas Corporation, Pasadena, Texas).

NYGLOS:Wollastonite with high length-diameter ratio is obtained from the Nyco of the Weir Si Baoluo of New York with trade name " NYGLOS-12 " Mineral products company (Nyco Minerals, Inc., Willsboro, New York).

TTD:It is public to derive from the uncommon love of Portland, Oregon, USA U.S. ladder for 4,7,10- trioxa -1,13- tridecane diamines It takes charge of (TCI America (Portland, Oregon)).

TS-720:The pyrogenic silica of processing can derive from Massachusetts with trade name " CAB-O-SIL TS-720 " The Bostonian Cabot Co., Ltd in state (Cabot Corporation, Boston, Massachusetts).

EH-30:Tertiary amine accelerators are obtained from New Jersey not Lip river Farnham Parker with trade name " VERSAMINE EH 30 " BASF AG (BASF Corporation, Florham Park, New Jersey).

Z-6040:3- glycidoxypropyltrimewasxysilanes are obtained from the DOW CORNING (Dow of available Corning, Midland, Michigan).

ADDUCT:At a temperature of 80-100 °F (26.7-37.7 DEG C), stirred to 40 gallons of 3 shaft types of (151.4L) Ross 80lbs (36.29Kg) TTD diamines is added in kettle, then adds 46lbs (20.87Kg) MX-154, and use anchor under a nitrogen Formula blade is mixed 30 minutes with 35rpm and shear-blade with 700rpm.Then, so that mixture is heated to 150 °F (65.6 DEG C), permit Perhaps mixture reaches its exothermic peak temperature about 190 °F (87.8 DEG C), is then further continued for mixing 10 minutes.Mixture is set to be cooled to 120 °F (48.9 DEG C) add the MX-154 of 27.6lbs (12.52Kg) and in nitrogen again under 80-100 °F (26.7-37.7 DEG C) Lower mixing 30 minutes.Then 150 °F (65.6 DEG C) are heated the mixture to and allow heat release again, are reaching exothermic peak temperature After remix 10 minutes.Then sealing container is transferred the material to.

Exemplary embodiments A

The part A for the two-part structure type adhesive composition that table 1 is listed is prepared as follows.

Part A

Other than the TS-720 pyrogenic silicas of about 40 weight %, all components of listing table 1 at 21 DEG C It is added in " 100MAX DAC " type speed mixing cup, and mixture is made to be dispersed in model " DAC with 1,500rpm 1 minute in 600SPEED MIXER ".Then remaining TS-720 is added, and continues to mix another minute with 1,500rpm, so Use " COWLES " type blade with 1,000rpm shear-mixeds 10 minutes afterwards.Then, in the vacuum of 28 inches of mercury (94.8KPa) Under, being mixed by using propeller mixer makes the part A composition of gained deaerate for 10 minutes.

Table 1

Part B

It is prepared by the part B of two-part structure type adhesive component shown in table 2.It will be all listed by table 2 at 21 DEG C Component is added in " 100MAX DAC " type speed mixing cup, and makes mixture with 1,500rpm in " DAC 600SPEED Evenly dispersed 2 minutes in MIXER ", then use " COWLES " type blade with 1,000rpm shear-mixeds 10 minutes.Then, exist Under the vacuum of 28 inches of mercury (94.8KPa), being mixed by using propeller mixer makes the part B of gained combine for 10 minutes Object deaerates.

Table 2

Embodiment 1 and embodiment 2

Part A composition is prepared in the method according to exemplary embodiments A, is a difference in that in capping but non-tight 10- gallons (37.85L) cylinder in, make the aluminum slice of about 50lbs (22.68Kg) at about 220-250 °F (104.4-121.1 DEG C) Four heat cycles are subjected in the baking oven of temperature 16 hours.Between each heat cycles, aluminum slice is set to be cooled to 21 DEG C, and move Except the aluminum slice of about 10lbs (4.54Kg).The aluminum slice used in Examples 1 and 2 is obtained after four heat cycles.

Part A and corresponding part B composition are uniformly mixed with following ratio by weight, and it is strong to evaluate impact peel Degree, T- peel strengths and lap shear strength.The results are shown in Table 3.

Exemplary embodiments A: 10.00/18.50

Embodiment 1: 10.14/18.50

Embodiment 2: 10.19/18.50

Assessment

Curable compositions are prepared as follows:At 21 DEG C, operating speed mixer is uniform by above-mentioned weight ratio with 1500rpm It mixes part A and part B forms 1 minute, then mildly manually mixed with wooden tongue depessor.In bead not included in preparation In in the case of, before assembling adhesive, globule is added to adhesive.

Impact peel strength

Impact peel strength is measured according to ISO 11343 as follows.Curable compositions are applied to " E60 EZG 60G The non-polished speciment of 2S " types derives from ACT test pieces Co., Ltd (the ACT Test of state of Michigan Xi Ersidaier Panels LLC, Hillsdale, Michigan), size be 0.787 × 3.54 × 0.030 inch (20.0 × 90.0 × 0.76mm).Coupon by with " GENERAL PURPOSE ADHESIVE CLEANER, 08987 " cleaning are de-gassed twice, Then (being all obtained from 3M companies (3M Company)) is ground with " 80+CUBITRON II ROLOC " grade abrasive disk, it is viscous to remove Close the electric galvanizing coating on surface.Adhesive sample thin layer is applied in 30mm × 20mm bonded areas of coupon, with³/₄- Before overlap joint is clamped together by inch (19.05mm) binder clip, smaller cohesive pearl is applied to an overlap joint.It is scraped using metal Knife removes extra adhesive.Before being tested with the impact velocity of 2m/s at -20 DEG C and/or 23 DEG C, the component of gained is made to exist Cure at 21 DEG C at least 7 days, in model " 9250INSTRON DYNATUP ", the minimal adjustment time at test temperature is 1 Hour.Area (25% to 90%, according to ISO 11343) under experiment curv is given energy to fracture (with Joulemeter).Impact Peel strength value is reported as impact strength (in terms of N/mm).Result listed by table 3 indicates each exemplary embodiments and embodiment The average value of at least two coupon.

T- peel strengths

T- peel strengths are measured according to ASTM D1876 as follows.Curable compositions are applied to away from end 1- inches 4 × 1 × 0.033 inch (101.6 × 25.4 × 0.84mm) 1018 cold rolled steel coupons block that (25.4mm) is bent with 90 ° of angles, And oil removing is simultaneously ground according to the method for impact peel test.Thin layer of adhesive is applied to 75mm × 25mm of coupon In bonded areas, in every side with two 1-¹/₄It, will smaller bonding before overlap joint is clamped together by inch (31.75mm) binder clip Pearl is applied to an overlap joint.Then, extra adhesive is removed using metallic spatula.Derived from Illinois Evans Wei Er MTS Systm Corp. (MTS Systems DEG C orporation, Evansville, Illinois) model " QTEST 100 " it is more With before pulling rate test on trial frame with 50mm/min, the component of gained is made to cure at 21 DEG C at least 4 days.It measures average Peeling force, and pulled at 2 to 5 inches (in terms of N/25mm) and report average value in range.Result listed by table 3 indicates each example The average value of the property shown embodiment and embodiment at least three coupon.

Lap shear strength

Lap shear is measured according to ASTM D1002 as follows.Make 4 × 1 × 0.033 inch (101.6 × 25.4 × 0.84mm) 1018 cold rolled steel coupons blocks deaerate, and the grinding as described in T- peel tests.Thin layer of adhesive is applied to coupon 12.5mm × 25mm bonded areas on, every side use³/₄It, will smaller bonding before overlap joint is clamped together by inch binder clip Pearl is applied to an overlap joint.Then, extra adhesive is removed using metallic spatula.It is drawn with 10mm/min on QTEST 100 Before dynamic rate test, the component of gained cures at least 4 days at 21 DEG C.Record inefficacy load.The lap shear strength provided It is calculated as:Inefficacy load/(length of the width x cohesive bodies of cohesive body).Result listed by table 3 indicates each exemplary embodiments With the average value of embodiment at least three coupon.

Table 3

In table 3, N/D means undetermined.

Under the premise of not departing from the spirit and scope of the disclosure, various modifications and change can be carried out to the disclosure.Therefore, The present disclosure is not limited to the embodiment above, but should refer to that is limited controls in by following claims and its any equivalent System.The disclosure can in a suitable manner be implemented in the case of not specifically disclosed any element in there is no the disclosure.

Claims

1. a kind of at least part of method preparing curable adhesive composition, the method includes:

It obtains and includes the aluminum slice of aliphatic acid grinding aid at least a part of the surface thereof, wherein the aluminum slice is previously It is ground;

The aluminum slice is heated;And then

2. according to the method described in claim 1, the wherein described component also includes toughener.

3. according to the method described in claim 2, the wherein described toughener includes core shell polymer, acrylic polymer, fourth At least one of nitrile rubber or polyurethane.

4. further including according to the method in claim 2 or 3, by least part of the curable adhesive composition It is packaged as two-part adhesive, wherein first part includes the amine hardener, and second part includes the curable epoxy tree Fat, at least one of the first part or the second part include the toughener, and the first part or institute It includes the aluminum slice to state at least one of second part.

5. according to the method described in claim 4, wherein including by least one of the curable adhesive composition It separates into the adhesive dispenser for including the first Room and second Room, wherein first Room includes the first part, and its Described in second Room include the second part.

6. method according to claim 4 or 5, wherein the curable epoxy has two or more epoxy groups Group and the amine hardener have two or more amine hydrogen, and the epoxy group on the curable epoxy and institute The molar ratio range for stating the amine hydrogen on amine hardener is about 0.5: 1 to about 3: 1.

7. method according to any one of claim 1 to 6, wherein the component includes the amine hardener, amine curing Agent includes aliphatic diamine, aromatic diamine, aryl alkylene diamines, polyether diamine or combinations thereof.

8. method according to any one of claim 1 to 6, wherein the component includes the curable epoxy, And the wherein described curable epoxy includes bisphenol epoxy, novolac epoxy resin or combination thereof.

9. method according to any one of claim 1 to 8, wherein the component also includes resist, plasticizer, silane At least one of coupling agent, thixotropic agent, pigment, reinforcing agent, clay or filler.

10. method according to any one of claim 1 to 9, wherein the heating is warm within the scope of 100 DEG C to 150 DEG C The environment setting of degree is lower to be carried out.

11. method according to any one of claim 1 to 10, wherein the aliphatic acid grinding aid includes stearic acid.

12. method according to any one of claim 1 to 11, wherein the aluminum slice is previously dry grinded.

13. method according to any one of claim 1 to 2, wherein the heating is described in packaging, shipment or storage It is carried out after at least one of aluminum slice.

14. method according to any one of claim 1 to 13, wherein the curable adhesive composition is at room temperature It is curable.

15. the method according to any one of claim 1 to 14, wherein relative to adhesive composition is compared, to described Aluminum slice, which is heated, to be provided when curing the curable adhesive composition with improved T- peel strengths or improvement The adhesive bond of at least one of impact peel strength, wherein the relatively adhesive composition and the curable adhesive group It is identical to close object, the difference is that the aluminum slice after milling without heating.